Magnesite refractory and method of making the same



Patented Feb. 1, 1927.

AUGUST MARKS, OF CARTERET, NEW

JERSEY, ASSIGNQR TO UNITED STATES Marlins-annu us COMPANY, A ooaroraarrolt or NEWuJERSEYJ MAGNESITE REFRACTORY AND METHOD MAKI NG TI-IE SAME.

. Nolirawing.

This invention relates to molded magnesite refractories and a method of making the same. .Magn esite' bricks and other'molded refractories possessmany very desirable qualities as high temperaturerefractories; and are very widely'u's'ed in metallurgical work. as for the lining offurnaces, converters. sottle'rs, ladles, etc., but have serious disadvantages in the susceptibility to crackingand crumbling or spalling, absorption of metals, and expansion when heated. Thepresent invention provides a magnesite brick or similar molded magnesite refractory wherein the spalling and expansion are much lessened, and a very durable and high quality of magnesite brick or other moldedrefractory is produced. The magnesite refractories according to' the present invention also, have a dense structure which is less absorptive of liquids-such as molten metalsand have less voids tha'n magnesite refractories heretofore in use. er

According to the present "invention .the

dnagnesitic body material is ground and otherwise prepared according to any suit;

able or known method for use in the manufacture of'refractories. The body material is then mixed with asuitable oil, such as .linseed oil, to form a plasti'cmass, being preferably well. mixed or lm'eaded, ,as is usual in the preparation of the plastic for molding bricks, retc. Prior to mixing with the oil. the body material is preferably dried at a temperature suflioient to drive ofl such excess moisture as may be contained therein.

The plastic mass is then molded into forms or shapes as maybedesired, as, for example, bricks, lining titles, crucibles. furnace shapes, muflies. retorts. zinc retorts. etc., the molding being preferably effected or completed under pressure in a hydraulic press.

YThe bricks, etc. are then subjected to a drying operation, to render them sufiiciently dry and firm to enable them to be properly burned. m J

The, molded articles are thentaken to a kiln or oven, stacked in appropriate and usual manner, and burned according to usual practue, the burning being preferably such Application filed June 8,

1926: Serial No. 114,566.

as to "produce what is known as a hard burned article, the temperature and time of burning being controlled by ,the nature K of the body material and such fluxes asmay be contained in the mix. In the heating, while the temperatures are gradually in- I creased at first, nevertheless the temperatures can bei'relatively quickly brought to the upper ranges as compared with the burning of articles formed from plasticscontaining water. 7

After burning .and cooling, the bricks, etc. are removed from the kiln ready for use. A variety of oils may be used. Vegetable oils such as linseed oil, cotton seed oil, etc. mav be'used; and certain animal oils suchas fish oil or other oils having similar properties, may be used. The resulting refractories have a greater density and hardness, less voids, a finer crystalline structure, a finer ring when struck, a less absorption of liquid metal, less ex-. pansion under heat and greater durabilityv in user, as compared --with others in the same class produced by previous methods. A specific example of the process, as applied to the manufacture of magnesite brick, will now be given. a Y

3 Dead burned magnesite (magnesite rock burned to drive oil the carbondioxid contained therein), preferably of the Austrian variety, is preferably first dried by heating to drive off such moisture as may be contained therein, and is then finely ground, In practice thefburnedmagnesite should be ground to a fineness such'that a large proportion will pass-through a screen of 100- mesh per lineal "inch. In general. the finer the size of the ground particles the better \vill be the refractory produced.

Linseed oilis then added to the'ground burned magnesite' and thoroughly mixed in a mixing pan to a plastic mass suitable for ,y molding. In practice one gallon of .oil may be used to about 117 pounds of magnesite. he amount of oil used may vary somewhat, however, depending on various factors.

The plastic mass is then put into forms or molds and subjected to a suitable pressure to form it into bricks, tiles, or other molded articles; it is preferable to.u se hydraulic pressure, as in the. ordinary molding of water-bonded magnesite bricks.

The bricks, etc. after molding are preferably subjected to a gradual drying process. The pressed bricks, etc. are then placed in a kiln and burned in the usual or any Wellknown manner.

The superior qualities of the resulting bricks, etc. appear to be due to the oxidation and decomposition of the oil. and the action of the decomposition products on the body material, which either effects an autogenous binding or produces substances which act as binders.

(The fOlBgOlllQ description is taken from my application Serial No. 754,983, filed December 10, 1924, of which the present application is a continuation, and which itreplaces, the present application being filed to introduce certain additional matter which is the result of subsequent experience inthe practice of the invention).

As the body material,- any suitable magnesite refractories may be used. Magnesite refractories are those made from magnesitic material, that is, Wholly or largely of magnesite. Suitable results are secured by using one-half Austrian and onehalf American magnesite. The magnesitic material requires to be dead burned, and

before grinding should be dried to drive ofi any excess of moisture which may be contained therein; but moisture not exceeding 0.5 per cent is not objectionable. It should be ground to such fineness that it will substantially all pass through a 20 or 30 mesh screen, and approximately half will pass through 21100 mesh screen. It is preferable for the best results that there should be a certain diversity in the size's'of the ground particles so that the finer particles may enter into the spaces or voids between the coarser particles, whereby to give the greatest density, strength and permanence to the brick. This result may be attained by mixing or blending magnesite of different degrees of fineness; or it may be attained by the common methodspt' grinding if the process is conducted skillfully to that end. A typical screen analysis of a suitable mate:

.rial. substantially all of which will pass through a. 20 mesh screen. will give approximately 40 per cent not passing through a 60 mesh screen, ahout'4-5 per cent passing terii'lediate sizes. 4

The oil to be used should be a siccative oil having fatty or lubricating properties. Linseed oil is preferable; and either raw or a 100 mesh screen, and the difference in in boiled oil may be used, accordingto choice, as hereinafter stated. Other vegetableoils;

having siccative properties resembling those of linseed 01]. may be used; and certain ammal o ls having-similar s ccative properties linseed oil in some suitable proportion.

Suitable oxidizingor catalytic dryerssuch as oxides of lead, cobalt, manganese, etc., may be used to accelerate the drying. In general, any good linseed oil substitute'may be used, of which several are known in the art, all of which are made up largely of sic'cative oils, and the best of which contain a considerable proportion of linseed oil. Mineral oils and petroleum distillates such as tar or the like, are unsuitable. But the lighter mineral oils may be used to a moderate extent as thinners; this, however, is needless with a suitably-chosen oil.

The proportion of oil used is important. The best amount of oil may vary with the nature and quality of the oil, the-fineness of the grinding of the magnesite, and the quality or origin of the magnesite. With magnesitic material of the nature and fineness hereinbefore stated, it is found that to 100 pounds of such material, good results are secured by using from five to seven pounds of linseed oil, and the best results with about six and one-half pounds of such oil, .or 6.5 per cent. With other oils or other grades of magnesitic material, the proportion should be varied according 'to cir cumstances to secure the best results, which can only be determined by experiment. Generally, if less than three or four per cent of oil is used, or if more than eight or nine per cent is used, failure will result. With too little oil, the body'material is not sufficiently bonded for proper molding and the molded. formscannot be properly hantic mass becomes too soft and sticky for proper molding and is liable to lose its shape before firing, and to blister during firing. I

After the oil is added-to the magnesite, these ingredients are to be thoroughly mixed.

until a homogeneous plastic, mass is produced.'-- This mixing is best done in the usual mixing pan or wet pan or pug mill. This mixing or pugging operation usually takes longer than for water-bonded magnesite: according to conditions it may take from one and one-half to three times as long to securea thoroughly hmnogc'neous blend. The plastic .mass may be immediately molded. or the molding may be delayed for some length of time. is desirable to cure theplastic mass before molding bv letting it stand a few hours.

or even a day. During this time the linseed hardens by oxidation and by reaction with magnesite constituent-s. so that the mass acquires greater coherence. This is desirable if the conditions are such oil partially In some instances it that the plastic is too soft and sticky for proper molding In practice, however, by using the best grade and fineness of body material and the mostsuitableoil, and the best percentage of oil to body material, a plastic mass may be produced which may be molded immediately or as soon as convenient. The molding of the bricks or other forms may be performed in any" usual molds orv molding press. While, successful results may be attained by molding by hand, and without a press or pressure otherwise than byv giving the mold follower a blow with a mallet, as is commonly doneby molders, yet

= the best results'are had by using a press,

preferably a hydraulic press, and imparting a pressure of from 1200 to 1500 pounds per square inch. This pressure .molding gives the greatest density and theleast porosity and absorptive property in the finished refractory.

i The bricks or other forms after being taken from the molds should then be dried to substantial hardness. Failure will result if the firing is performed before the bricks are adequately dried. This drying may bevariously performed, but it is suitable to expose the bricks or other articles in the open air, stacking them so that they are separated from one another and exposed on all sides except the bottom to the air. During the drying, the hardening of the brick by the siccative action of the oil conti'nuels progressively until the brick has become thoroughly dry and sufliciently hard all through. As soon as the bricks are, {firm and dense and to all appearance dryj they may at once go into the kiln for burning; but better results are secured by subjecting the bricks to a prolonged period of drying, which may continue for a week or more, or as long as it is cdnvenient to store the bricks in the manner stated; During; this prolonged drying the hardening of the brick by the completion of the siccative action of the oil is effected, and the brick becomes thoroughly dry and hard all through; it then is apparently as hard and dense as an ordinary water-bonded: brick which has been burned. Under test it exhibits a considerable approach toward the strength of such burned magnesite bricks.

These unburned bricks may be built into a furnace or converter asthe lining thereof, and accord in most instances quite as desirable a lining as the ordinary waterbonded burned magnesite brick. The bricks become fired in the heating up of the furnace or converter, and this method gives very good results. (Theunburned oil-bonded magnesite bricks thus produced are not claimed in the present application,

being the subject of a separate application filed May Q, 1926, Serial No. 107,307).

The pressed and dried bricks produced preferably -ih the manner hereinabove described are then fired by placing in a kiln and burning in the usual or any wellknown manner. The burning of the bricks requires no different treatment from that of the ordinary Water-bonded magnesite' bricks. From the first firingup until the final coolingv down and unloading, requires, as usual, about ten or twelve days. The temperature required is substantially the same 'as for water-bonded magnesite bricks, rising gradually to a maximum of say from 1400 to 1500 The 'magnesite bricks produced are smooth, regular in shape, hard and dense, and consist of a mass of small interlocked crystals, and, as before mentioned, the. bricks are very durable, and cracking and spalling, expansion under heating, absorption of liquid metals, and corrosion by metals or gases, are very materially lessened. Ma-gnesite bricks produced according to the present invention are found to have on the average a lower percentage of voidsand a smaller coefficient of expansion as compared with the best grades of magnesite bricks manufactured, by present methods. The life of these bricks as compared with the ordinary water-bonded mag nesite bricks is decidedly greater, but the difference depends so much upon local-or special'conditions that it is difficult to state it with exactness. Incopper refining, where the bricks are exposed at and below the level of the molten metal, they endure for more than twice, and insome cases from four to six times, as, long as the ordinary bricks used under similar conditions. When not exposed to molten metal their life exceeds that of ordinary magnesite bricks by from two to six times. I

In the .use of linseed oil, as to whether raw or boiled oil should be used depends upon the procedure which it is desired tofollow. In a works equipped for-producing water bonded magnesite bricks, it will be most convenient to use raw 'oil, in which case the mix will be in usual course left in a storage bin for a few hours to properly cure or set, and then molded in the usual and later. gradually to dryer air and higher heat, until they are fully dried. The total period of drying may vary according to circumstances, but will ordinarily take from to hours. At the end of this drying or curingoperation the brick is firm and dense, and to all appearances dried. It is, however, desirable to thereafter sub e ct the br'cks to a somewhat .prolonged drying in the open alr, which may continue for several days, or: as long as convenient.

do not require to be passed through a dryer,

but may be dried readily in the open air. A drying of about one day is sufficient for curing, after which the bricks may be'immediately fired; but it is advantageous to prolong the drying for several days, if it is convenient to thus store the molded bricks.

Advantageous results are secured by using a mixture or blend of raw'and' boiled oils, for which purpose "from one quarter to onethird of boiled oil results when mixed with the magnesite in producing a plastic mass which may be molded almost immediately,

although even then it is advantageous to let the mix cure for 'a short time before molding. Another way inwhich raw oil may be successfully used is to preliminarily heat the oil for a few hoprs at a temperature of 100 (1., whereby it is conditioned to a sufficient approximation to boiled oil to produce a plastic mass which is not too sticky for immediate molding. This conditioning, however, 'may be better effected after admixture with the magnesite, either by leaving the mix to cure, or by moderate heating; in either case the raw oilassumes the properties of boiled oil, -The same conditioning result is secured after the molding by heating the molded (bricks in the dryer; It is thus a matter of choice or convenience in the manufacture as to Whether the linseed oil is first boiled or otherwise conditioned be- 7 fore mixing; or is mixed in the raw state with magnesite, and the plastic mass left standing for a suflicient time; or a blend of raw and boiled oils isused; or however the plastic mass may be brought to condition for molding, the conditioning may be performed by heating the molded bricks. Thus, the necessary conditioning orcuring may take place either before the oil is used or after its admixture with the magnesite, or even after molding, the precise method being governed largely by convenience and the desired manufacturing procedure.

The properties valuable in the oil bindlelr are: (1 That the oil be a fatty oil, t e characteristic of which is its ability to' penetrate into the pores of dr substances soas to wet,the surfaces of th. particlesthere;

of. The oil thus covers the grains with a film. (2) That the oil have an effective lubricating property, so that it enablesthe particles to slip past one another both in the mixing pan and under pressure in the molds, thus enabling the pressure to compactthe particles closely together to afford in the mass the maximum density and'the mininuin-porosity. This is partly due, when the 'mat'erfal is ground to varying degrees of fineness, as above described, to the finer particles entering intov the voids be-- tween" the coarser particles and substantially filling these voids. (3) That the oil give plasticity to the magnesite, which is by it constitutes a self-hardening bond be-.

tween the particles, so that the bricks, after being molded and before burning, gradually harden. Apparently any oil having this siccative' property to a suitable degree has also the other properties first mentioned. (5) That the oil have a reaction with constitutents of the magnesitic body material, whereby an effective permanent bond is afforded. It is found that such reaction occurs between linseed oil and dead-burned magnesite, forming products which cement together the particles of magnesite.

While the various actions accompanying the use of such oil are not definitely deter- .mined, there is reason to believe that the following take place :During the mixing the oil coats the grains injthin films and thereby comes into intimate contact with .the finely-divided magnesite. Spontaneous oxidation sets in, wherein the esters of the oil unite with oxygen,mainly from the atmosphere,which together with other reactions, generates heat. The described mixture of magnesite and oil standing for 24 hours at atmospheric temperature develops an increased temperature of 10 C. or more, with the evolution of a trating odor, Tests of linseed oil alone and mixed with magnesite show a considerably I higher acquired temperature in the mixture than in the oil alone, indicating a reaction peculiar to,,the magnesite; (this is confirm ed by tests of mixtures of'the oil with pulverized fire-clay brick (an inert material) with which under dike conditions the in-' creased temperature was 6 C.). .It is known thaton oxidation of linseed oil there is an increase ofits acidity, "by development of unsaturated fatty acids, and in the presence ofbases this results in saponification. Magnesite contains mainly MgO, with small proportions of other bases,-and these su" ply the basic material for neutralizing tlie acids developed in the oil, the resulting salts being intimately distributed throughon the product. Thus the result .of combining linseed oil with magnesite is that an aggregate of the magnesite particles is produced, the particles being cemented together not-only by the hardened oil, but also by .the magnesitic salts which result from the ;reaction of the fatty acids with MgO and other bases in the magnesite. What occurs durin'gthe burning of the bricks cannot be exactly stated, but apparently in addition to the carbonization of the hardened oil the pungent and penemagnesite salts are reduced to their mineral constituents, with perhaps some crystallizing action, whereby they enter into permanentrelation with the constituents of the magnesite and contribute largely to the formation of a permanent bond..

' As compared with the standard method of producing magnesite bricksby a'bond of water, the presentinvention has important advantages. With a water-bonded brick the water causes hydration of MgO, resulting in enlargement due to the greater mass of the magnesium hydrate, which tends to crack the brick. In the water-bonded brick during drying and burning a certain volume of steam is produced, partly at a high temperature, by the decomposition of Mg (OH) which is liable to disrupt "the structure, producing minute fissures which subsequently under temperature changes lead tothe cracking and spalling of the bricks. With the oil-bonded brick, on the contrary, any

traces of free'moisture and the chemicallycombined water are expelled at comparatively low temperatures. There is no tendency to enlargement or to the formation of fissures, if the method is correctly followed.

Microscopic and petrogra hic examination of bricks made of precise y like magnesite mixes ground'to the same finenesses and treated alike throughout, except thatth one was made with a water-bond in the ordinary manner, and the other with an oil bond ac- 40 iron oxide, and were firmly cemented tocording to the present inventionfgave the following results (1) The water-bonded brick was composd of grains of periclase averaging about 0.15 mm. cemented with crystalline matter having the characteristics of olivine (forsterite) and monticellit-e. The individual grains were saturated with gether into aggregate groups, but the groups or aggregated grains were not so Well bound together,-.so that the brick was somewhat friable. (2) The oil-bonded brick was found-to have very much finer grains of peripears clase, their average diameter being 0.04 mm. The iron oxide Was 1nuch less and existed as minute specks of m'agnsio-ferrite, within the grains of periclase. The individual graihs and the groups of grains were well cemented together with crystalline matter in the nature of forsterite and monticellite. The oil brick hadla finer, denser, better burned and better cemented texture than the water brick. The pores or voids in the water brick were very much larger than in the oilbrick. An important differenc between the structure of the bricks was found to be that in the oil-bonded brick,

the iron constituent of the magnesite was rediiced during burning to the basic oxide;

which in turn combined with the magnesia resent to form magnesio-ferrite', whlch ap to be an important element in the binding medium of this brick. The fact that in the oil-bonded brick the grains or particles are more closely-bound together, and that r the iron exists in combination with magnesia, gives these bricks a more dense characteristic and a more uniform composition than exists with water-bonded bricks; the resulting denseness causes the oil-bonded bricks to' be less porous and less absorptive, and their more uniform composition greatly reduces spalling and cracking.

, Lam aware that various pulverulent body materials, including magnesite, have been proposed to be united by a temporary bond of some adhesive material of a gummy, mucilaginous ,or tarry nature, and that boiled linseed oil has been suggested as such a temporary bond; but such bond is used merely to unite the particles of the non-plastic vmaterial so that it may be molded, and until the temperature is attained at which the particles will be united by the fiux produced by heating them; such temporary bonds burn away and do not appreciably affect the com- "position of the bricks. According to my 1, The described dense molded magnesite refractory formed from a magnesitic .body

material whichhas' been mixed with a siccative oil, molded, dried and burned.

2.,The described dense molded magnesite refractory composed of a ln agnesitic body material and a permanent binder comprising linseed oil products, burned.

3. The described molded magnesite refractory composed of a magnesitic body mamolded, dried and '"terial and a permanent binder formed from a siccat'ive oil, said oil being in proportion approximating -5 to 7 percent of the body material, molded, dried and burned.

4. The described dense molded magnesite refractory, formed from a body material comprising dead-burned magnesite of different degrees of fineness, mixed with a lubricating fatty bonding oil, molded, dried and burned, the finer particles of the body material being within-the spaces between the coarser particles. L

5. The described molded magnesite refractory formed from a magnesitic body material of different degrees of fineness, mixed. with bonding oil having the properties of penetrating the dry material, coating its particles with a film, lubricating them so that they enter closely together, and whereb the mixture is made plastic, and molde, dried and burned.

6. The described dense magnesite. brick. formed from dead-burned 'magnesite and a siccative oil, molded, dried and burned.

7. The described dense magnesitebrick formed from dead-burned magnesite and linseed oil, molded, dried and burned.

8. A magnesite brick formed from deadburned magnesite and linseed oil, the oil in the proportion of approximately 5 to 7 per cent, molded, dried and burned."

9. A magnesite brick formedfrom deadburned magncsite and linseed oil, the oil in the proportion of approximately 6.5 per cent, molded, dried and burned. I

10. A dense magnesite refractory having a small percentage of voids and low absorp tion of liquid metals, composed of magnesite of varying',degrees of fineness," bonded by linseed oil products, molded, \dried and burned.

11. The described method of making magnesite bricks or molded refractories, comprising mixing a pulverized magnesitio body material with a permanent-bonding siccative oil, molding, curing the molded article and burning.

12. The described method of making magnesite bricks or molded refractories, comprising mixing a pulverized magnesitic body material With a siccative oil, molding, drying the molded article to hardness and burning.

13. The described method of making magnesite bricks or molded refractories,

' material with linseed oil, molding, curing the molded article and burning, 1

14. The described method of making magnesite bricks or molded refractories, comprising mixing a pulverized magnesitic body material of different degrees of fineness with a lubricating fatty oil, molding, drying and burning. 15. The described method of making magnesite bricks'or moldedrefractories, comprising mixing a pulverized magnesitic body c0mpris-' 111g mixing a pulverized magnesitic body.

material of'difiierent degrees of fineness With a lubricating fatty oil, uniting them by prolonged Workingto produce a plastic mass, molding, drying and burning.

16. The method of making magnesite bricks or molded refractories, comprising mixing pulverized magnesite with linseed oil, molding, curing the molded article and burning. I, i

-17. The method of making magnesite bricks or molded refractories, comprising mixing pulverized magnesite with linseed oil, molding, drying the molded article to hardness and burning.

18. The method of making n'iagnesite bricks or molded refractories, comprising mixing pulverized magnesito ,with linseed oil in a proportion approximating 5 to 7 per cent, molding, drying and burning.

19. The method of making inagnesite' bricks or molded refractories, comprising mixing pulverized magnesite with linseed oil in a proportion approximating 6.5 per cent molding, drying and burning.

20. The method of making magnesite tion will pass a 100 mesh screen, and a large proportion Wlll not pass a (30 mesh screen,

with a binder of a fatty siccative oil, molding under pressure to cause the finer particles to enter the spaces between thelarger par-- ticles, drying and burning. In witness whereof, I

signed my name.

" AUGUST MARKS. i

have hereunto 

